2-acetamido-5-methylbenzenephosphonic acid diethylester

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-acetamido-5-methylbenzenephosphonic acid diethylester
• 英文别名: N-(2-diethoxyphosphoryl-4-methylphenyl)acetamide
• 化学式: C₁₃H₂₀NO₄P
• 分子量: 285.28
• InChiKey: AAYGGVTUINOBHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-acetamido-5-methylbenzenephosphonic acid diethylester 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 24.0h， 以51%的产率得到2,5-dimethyl-3H-1,3-benzazaphosphole
  参考文献：
  名称：

  Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects

  摘要：

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01019-5
• 作为产物：
  描述：

  2'-溴-4'-甲基乙酰苯胺 、 亚磷酸三乙酯 在 nickel dichloride 作用下， 以85%的产率得到2-acetamido-5-methylbenzenephosphonic acid diethylester
  参考文献：
  名称：

  Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects

  摘要：

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)01019-5

文献信息

• Synthesis of 1H-1,3-benzazaphospholes: substituent influence and mechanistical aspects
  作者：Joachim Heinicke、Nidhi Gupta、Anushka Surana、Normen Peulecke、Brigitte Witt、Kinga Steinhauser、Raj K Bansal、Peter G Jones

  DOI：10.1016/s0040-4020(01)01019-5

  日期：2001.12

  Various substituted carboxylic acid 2-chloro- and 2-bromoanilides 1a-j react with triethylphosphite in the presence of anhydrous NiCl2 or NiBr2 to give o-acylamido-benzenephosphonic acid esters 2a-g and 2j. Yields depend strongly on the substituents. 2-Fluoro-4,6-dibromoacetanilide 1g reacts only at 6-position, indicating an o-directed process. Based on substituent effects, we infer a mechanism via Ni(0) intermediates that insert into the carbon-halogen bond. The N-tertiary 2-bromoformanilide 4 does not undergo phosphonylation to 5 in the presence of the Ni-catalyst but reacts in the presence of Pd-catalysts. The subsequent reduction of the N-secondary o-acylamido-benzenephosphonic acid esters 2 with excess LiAlH4 is coupled with an intramolecular cyclisation to the 1H-1,3-benzazaphospholes 6 whereas the N-tertiary derivative 5 does not undergo cyclisation upon reduction. NMR data and the crystal structure of 6d are reported. (C) 2001 Elsevier Science Ltd. All rights reserved.